N-(halogen substituted alkenyl) polyhalobenzamides



3-bromo- 2'-penteny l, 2,3;dichloroallyl,

United States Patent 3,077,498 N-(HALOGEN SUBSTITUTED ALKENYL) POLYHALOBENZAMIDES Joseph W. Baker and JohnP. Chupp, Kirkwood, Mo., assignors to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Filed Aug. 18, 1959, Ser. No. 834,423 4 Claims. (Cl. 260558) wherein X and Y are halogens, preferably chlorine, although other halogens may be used; n is an integer of from 1 to 4, provided that when n equals 1 then Y is in the number 6 position on the ring; and R and R each represent a halogen substituted lower alkenyl radical containing one double'bond having'halogen linked to unsaturated carbon.v

Examples of'lower alkenyl groups include 2-chloroallyl, 2-iodoallyl, Z-bromoallyl, 2-chloroisopropenyl, 3-=

chloro-Z-butnyl, 3-iodo- 2-buteny1, 3-chloro- 2-pentenyl, 2-3-dibromoallyl, 2-chloro-3-fluoroallyl, 2,3-dichloro-2 -butenyl, 2-chloro-3- ;.bromobutenyl, etc, I lncluded within the above class of compounds is a preferred group which have the structure and R each represent a chloroallyl radical in which the chlorine is attached to an unsaturated carbon. The compounds of this invention may be prepared by 'the reaction of apol yhalobenzoyl halide, preferably the chloride, with the appropriate amine. be carried out in solution in an organic solvent and in the presence of a hydrogen chloride acceptor e.g. a tertiary amine, or an excess of the amine reactant. Similarly the reaction can be carried out in aqueous media, as for example, in a dilute aqueous solution of sodium carbonate (HCl acceptor). Because of the exothermic nature of the reaction, it is preferred to slowly add the acid chloride to the solution of the amine and hydrogen chloride acceptor. After the addition of the acid chloride is complete, and the reaction mixture has been agitated for a short period e.g. 30 minutes to 1 hour, the N,N-di-haloalkenyl polyhalobenzamide can be recovered from the reaction mixture by any means known to those skilled in the art. For example, the product may be extracted from an aqueous reaction mixture by the use of a suitable organic solvent, e.g. methylene chloride; the product is then recovered by stripping off the organic solvent at subatmospheric pressures.

The following examples illustrate the preparation and properties of some of the new compounds of this invention but are not to be taken as a limitation thereon.

wherein R Example 1 N,N-BIS(2-CHLOROALLYL)-2,3,6- TRICHLOROBENZAMIDE To a suitable reaction vessel containing 18.2 grams (0.11 mole) of N,N-bis(2-chloroallyl) amine and 11.7 grams (0.11 mole) of sodium carbonate in 150 ml. of water, there is added dropwise with stirring, 24.4 grams (0.1 mole) of 2,3,6-trichlorobenzoyl chloride. After the This reaction can '5 stripped off up to 60 Cat 8 mm. Hg. absolute pressure. A liquid product is recovered which is indentified as N,N- bis(2-chloroallyl)-2',3,6'-trichlorobenzamide and is obtained in 83% theory yield. Analysis: 1

10 I Calculated Found Chlorine 47. 4 49. .5

Using the procedure of Example 1, except bysubstituting an'equivalent amount ofthe following slectnuzlary amines (column I) for the N,N-bis(2-chloroallyl) amine of said example, a'good yield of the 'following N,N-bis (haloalkenyl)-2f,3',6-\trihalobenzamides (column II) are obtained.

Exiaqmple Column-I, Amine Reactant Column II, Product 2 N, N his (2 brornoallyl) N,N-b ls(2-brornoallyl) amine. gififltitrichlorobenzam- V trichlorob'enzarnide.

4 N,-N-bis,(3-chloro-2'-bu- N,N.-bist3 chloro 2-butenyl) tenyDamine if},3f,6-trichlorobenzam roallyl) amine. allyl)-2,3,6?-trichloro- I 4i N-2-ehloroallyl-N-2,3-di- N-2 ohloroallyl-N-2,3-dichloroallyl amine. chloroai1y1-2,3,6-triehlo,

robenzamide.

7 N,N-blS (2, 3-dichlol'0allyl) N,N-bis (2,3-diehloroallyl)- amine. 2&3 ,6 trichlorobenzama N, N-bis (2, 3-dichloro-2-bu- N,N-bis(2,3-dichloro-2-buvtenyl) amine. teuyl)-2,3,6-trichloro- 9 N-Z-chlorOallylN-li-ehlo- N-2-cbloroallyhN-il-chloroe ro-2-buteny1 amine. ,2-butenyl-2,3,6'-trich1orobenzarrlde.

10.; N-2-iodoallyl-N -3-chloro: N-2-lodoa1lyl-N-3-chloro-.

allyl amine. allyl-2,3,6'-trich1oro-. 1

benzamide.

" Example 11 Employing the procedure of Example 1 except by,-snbstituting an equivalent amount of 2,6-dichlorobenzoyl chloride for the 2,3,6-trichlorobenzoyl chloride, a good yield of N,N-bis(2chlorallyl)-2',6-dichlorobenzamide is obtained.

Employing the procedure of the foregoing examples, except by substituting the trichlorobenzoyl chloride with an equivalent amount of the following trihalobenzoyl chlorides, the following trihalobenzamides are prepared:

Example ColumnIBenzoyl Column II Amine Product No. Chloride Reactant 12 2,3,6-triiodo ben- N,N-bis(2-bro- N,N-bls(2-brozoyl chloride. moallyl) amine. moallyl)2,3,6-

triiodobenzamide.

13 2-ch1oro,3,6-dibro- N,N-bis(3-chloro- N,N-bis(3-ch1oromobenzoyl 2-butenyl) 2-butenyl)2- chloride. amine. chl0ro-3,6

dibromobenzamlde.

6 5 chloro benzoyl chloroallyl) chloroally1)2 chloride. amine. fiuoro-'i-6-dichloro benzamide.

15 2,3,4-trichloro N,N-his(2-ohloro- N,N-bis(?ch1orobenzoyl chloride. allyl) amine. allyl)-2,3,4'

trichlorobenzamide.

16 2,4,5-trlchloro- ....do N,N-bis(2-ehlorobenzoyl a1lyl)-2,4,5'- chloride. trichlorobenzamide.

Patented Feb. 12, 1963 addition of the benzoyl chloride is complete, the reaction mixture is stirred at about The product is then extrac of methylene chloride.

50' C. for about 50 minutes. ted with four 50 ml. portions The methylene chloride is Example ColunmIBenzoyl ColumnIIAmine Product No. Chloride Reactant 17 2,3,5-trichloro- N,N-bis(2-chloro- N-N,bis.(2-ehl0rochloride. trichlorobenp 18.. 2,3,4,5-tetrachlo- N,Nbis,2-bromo- N,N-bis(2-bron1o'- rbbenzoyl allyl) amine. allyl) 2,-3,4',5-

chloride. tetrachlorobenzamide.

19 2,3,5,G-tetrachlo- N,N-bis(3-ehlor0-1 N,N-bis(3-chlororobenzoyl Z-butenyl) 2-butenyl) chloride. amine. 2,3,5,6-tetrachlorobenzamide 20 'Pentachloroben- N,N-bis(2-chloro- N,N-bis(2-chlorozoyl chloride. allyl) amine. allyl) pentaglorobenzam-s.

21 2,3,4,6-tetrebro- N,N-bls(2,3di- N,N-bis(2,3-d1- mobcnzoyl chloroallyl) chloroallyl) chloride. amine. -2,3,4,6-tetra- I bromobenz- 22 2,3,4,6-tetrachloro- N-2-chloroallyl- N-2-ehloroa1Iyl-- I benzoyl N-2,3-dichloro- N-2,3-diehlorotetrachlorot benzamide.

23 2,4,5,6-tetrachlor0- N,N-bis(2-chloro- N,N-bis(2-chlorobenzoyl allyl) amine. a1lyI)-2,4,5,6-' if a... chlorlde. tetrachlorobenzamide.

24 .2,3,4-trlbromo- N,N-bis(2-chloro-. N ,N-bls(2-chlorobenzoyl B-tluoroallyl) B-fluoroallyl) chloride. amine. 2,3,4'-tribromobenzann'de.

, The compounds of this invention have a wide variety or biocidal uses.- For example, N,N-bis(2-chloroallyl)- 2",3",6'-trichlorobenzamide gave a 90% kill in the yellow fever mosquito larvae test (10 ppm. or 0.001% aqueous solution' for 24 hours). Defoliant action is also obtained,

e.g. 76-'-100% defoliation occurs when a solution containing 0.05% of N,N bis(2 chloroallyl)-2,3,6';trichloro benzamide is applied to bean plants containing one mature trifoliat and one partially opened trifoliat (observation is made 14 days after spraying). The compounds of this'invention are also useful for inhibiting the germip This pre-emergence herbicidal use, is covered in our copending application SerialNumber 834,422, filed August Although this invention has been described with respect to certain specific embodiments, it is not so limited grass or rye grass is present and it is to be understood that variations and modifications thereof obvious to those skilled in the'art maybe made without departing from the spirit or scope of this invention.

What is claimed is: w

1. A compound of the structur wherein X and Y are halogen atoms, n is an integer of from 1 to 4, provided that when n equals 1 then Y is in 'the number 6 position on the ring; and R and R each References Cited in the file of this patent UNITED STATES PATENTS 2,326,471 Lontz -...Ang. 10, 1943 2,412,510 Jones Dec. 10,1946 2,551,891 Martin et a1. May .8, 1951 2,687,403 Ballard et a1. Aug. 24, 1954 2,726,947 Baumgartner Dee. 13, 1955 FOREIGN PATENTS 812,376 Germany Aug. 30, 1951 OTHER REFERENCES Beilstein Handbuch der Organische Chemie, vol. 9, 1926, .204. p p Bottger et al.: Preliminary Test of Chlorinated Benzamides as Insecticides, U.S. Dept. of Agriculture Bulletin No. E-789 (1949), pp. l-21, pages 5-8 relied on;

Handbook of Chemistry and Physics (35th ed.), pub.

by Chemical Rubber Pub. Co. (Cleveland) 1953), pages 

1. A COMPOUND OF THE STRUCTURE 